EP1841705B1 - Sealing materials and devices utilizing such materials - Google Patents

Sealing materials and devices utilizing such materials Download PDF

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Publication number
EP1841705B1
EP1841705B1 EP06733746A EP06733746A EP1841705B1 EP 1841705 B1 EP1841705 B1 EP 1841705B1 EP 06733746 A EP06733746 A EP 06733746A EP 06733746 A EP06733746 A EP 06733746A EP 1841705 B1 EP1841705 B1 EP 1841705B1
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EP
European Patent Office
Prior art keywords
glass frit
sealing
glass
zno
sealing material
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
EP06733746A
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German (de)
English (en)
French (fr)
Other versions
EP1841705A4 (en
EP1841705A2 (en
Inventor
Jeffrey E. Cortright
Robert M. Morena
Lisa A. Lamberson
Pamela A. Maurey
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Corning Inc
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Corning Inc
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Publication date
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Publication of EP1841705A4 publication Critical patent/EP1841705A4/en
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/24—Fusion seal compositions being frit compositions having non-frit additions, i.e. for use as seals between dissimilar materials, e.g. glass and metal; Glass solders
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0271—Sealing or supporting means around electrodes, matrices or membranes
    • H01M8/028—Sealing means characterised by their material
    • H01M8/0282—Inorganic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
    • H01M2008/1293—Fuel cells with solid oxide electrolytes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • the present invention relates generally to glass sealing frits such as alkali-zinc-silicate frits, and seals and devices utilizing such frits. More specifically, these frits and sealing materials are suitable as sealing frits in solid oxide fuel cells (SOFC).
  • SOFC solid oxide fuel cells
  • Frits which seal in the temperature range of 600°C to 1000°C represent an intermediate class of materials between the B 2 O 3 or P 2 O 5 based frits used for low temperature sealing of many commercial glass products and the diverse number of silicates utilized for high temperature joining of advanced ceramic, structural components.
  • the low temperature frits are used at temperatures below 600°C for sealing products such as cathode ray tubes (CRT), light bulbs and the like.
  • the high temperature frits are used at temperatures above 1000°C to produce articles which may embody high temperature, fiber reinforced, structural ceramics.
  • a very old product in the intermediate temperature range (600°C to 1000°C) of sealing is ZnO- B 2 O 3 -SiO 2 frit.
  • Another is Li 2 O-modified ZnO- Al 2 O 3 -SiO 2 frit designed for use between 900°C to 1000°C. Frits that seal in the range of 600°C to 800°C are important for many applications. The need for such frits became evident through requests for sealant frits for solid Oxide fuel cells (SOFC).
  • SOFC solid Oxide fuel cells
  • fuel cell devices undergo large thermal cycling and large thermal gradients, which induces thermal stresses in the fuel cell stack components.
  • the seals need to be able to withstand high temperature fluctuations and have expansion coefficients compatible with electrolyte sheets and frames.
  • JP 03 183638A describes a weather resistant glass for sealing stainless steel, which comprises by weight 50-70% SiO 2 , 1.5-10% Al 2 O 3 , 2.0-10.0% B 2 O 3 , 16.0-28.0% R 2 O (R is Li, Na or K), 2.0-15.0% R'O (R' is Mg, Ca, Sr, Ba or Zn) and 0-1.5%ZrO 2 .
  • US2005/0277541 describes a sealing glass frit for stably joining metal members or ceramic members having a composition (in mole%) of 40-70% SiO 2 , 5-20% Al 2 O 3 , 4-20% Na 2 O, 4-20% K 2 O, 5-20% ZrO 2 , the total content of Na 2 O and K 2 O being not lower than 12 mol%.
  • EP-A-0 982 274 describes sealing glass frits based on high strain point/high CTE alkali-zinc-silicate glass compositions, that do not comprise B 2 O 3 and consist essentially of (in weight%) 50-70% SiO 2 , 0-5% Al 2 O 3 , 0-5% Li 2 O, 2-10% Na 2 O, 5-15% K 2 O, 10-25% ZnO, 0-10% BaO, 0-5% TiO 2 and 0-10% ZrO 2 .
  • U.S. Patent 6,291,092 describes the B 2 O 3 -free- frit seals suitable for use in solid oxide. These frit seals had been successfully used in many applications. However, some of the fuel cell devices utilize steel components (e.g., frames or substrates).
  • sealing material of the present invention seals fuel cell device components at temperature ranges (700-900°C) while having CTEs that are compatible with the CTEs of these components.
  • Another advantage of the sealing material of the present invention is that the resultant seals are durable in the SOFC environments.
  • a solid oxide fuel cell device incorporates a sealing material resistant to hydrogen gas permeation at a sealing temperature in the intermediate temperature range of 600°C -800°C , the seal having a CTE in the range of 100x10 -7 /°C to 120x10 -7 /°C, wherein the sealing material comprises in weight %, of:
  • a solid oxide fuel cell device sealing material comprises frit glass in mole %, of: SiO 2 70-85 ; Al 2 O 4 1-3; Na 2 O 0-8; K 2 O 10-20; ZnO 0-10; ZrO 2 0-6; MgO 0-7; and TiO 2 0-2.
  • this frit glass when mixed with filler and then fired, forms a seal that is resistant to hydrogen gas permeation at a sealing temperature in the intermediate temperature range of 600°C -800°C, the seal having a CTE in the 100x10 -7 /°C to 120x10 -7 /°C.
  • Figure 1 is a schematic perspective view of an exemplary solid oxide fuel cell device assembly
  • Figure 2 is an exploded, perspective view of a portion of the solid oxide fuel cell device assembly of Figure 1 ;
  • Figure 3 is a perspective view of an exemplary fuel cell device.
  • Figure 4 illustrates the temperature behavior of exemplary glass frit/filler blends.
  • FIG 1 is a perspective view of a typical SOFC device assembly 10.
  • Figure 2 illustrates a portion of the fuel cell device assembly 10, including stacked fuel cell devices 12 .
  • the SOFC device assembly 10 includes alternating fuel cell devices, each composed of layers of a solid electrolyte, cathode and anode plates.
  • the solid electrolyte generally is yttrium (Y)-doped ZrO 2 .
  • Fuel cell devices 12 include anodes 14, cathodes 16 and an electrolyte (not shown).
  • Each fuel cell device 12 also comprises distribution member 18 which embodies a plurality of parallel passages 20 for the supply of electrolyte, oxidant or fuel.
  • the axes of passages 20 lie in a common plane.
  • Distribution member 18 is preferably manufactured from two corrugated, ceramic plates.
  • the corrugations of the plates are arranged parallel, and the troughs of one of the plates are bonded to the peaks of the other plate. This forms passages 20 which have a diameter on the order of 2 mm.
  • porous support structure 22 surrounds and extends transversely of distribution member 18. It contacts the peaks and the troughs of member 18 to form a plurality of parallel passages which are anode 14 or cathode 16 chambers of solid oxide fuel cell devices 12. They provide the distribution and removal of the electrolyte for solid oxide fuel cell devices 12.
  • the corrugated ceramic plates have apertures between passages 20 to allow fuel to flow from passages 20 into anode 14 or cathode 16 chambers of solid oxide fuel cell devices 10.
  • Figure 3 is an exploded, fragmentary view showing alternating anodes 14 and cathodes 16 and their relationship to passages 20.
  • the glass-frit-based seals of this invention may encapsulate each cell 12, or they may form a barrier between each cell 12, a group of cells, or a component incorporating one or more cells 12.
  • the glass-frit-based seals may take the form of a plate sandwiched between adjacent cells 12.
  • Structure 22 also may be made of the glass frits of this invention.
  • the glass-frit-based seals prevent hydrogen gas from diffusing from one cell 12 (or a group of cells) to another.
  • the glass-frit-based seals may be used in SOFC devices with different architecture than that shown in Figures 1-3 , any place where one or more SOFC device components need to be sealed to another component
  • the solid oxide fuel cell device 10 incorporates a sealing material resistant to hydrogen gas permeation at a sealing temperature in the intermediate temperature range of 600°C -800°C.
  • the sealing material has a CTE in the 100x10 -7 /°C to 120x 10 -7 /°C.
  • the sealing material comprises sealing glass frit in 75 to 95 (preferably 80 to 90) weight % and mill addition, for example an alumina mill, zirconia mill or leucite mill addition, 5wt % to 25 wt% (preferably 10 to 20 wt%), such that total wt % of glass frit and the mill addition is 100 wt%.
  • mean particle size of the addition be less than 5 ⁇ m, more preferably less than 1 ⁇ m, and most preferably, be less than 0.5 ⁇ m.
  • the sealing glass frits of this invention do not contain B 2 O 3 , and have either no ZnO, or a relatively small amount of ZnO.
  • the sealing glass frits comprise in mole percent of: SiO 2 70-85 Al 2 O 3 0-5 Na 2 O 0-8 K 2 O 10-25 ZnO 0-10 ZrO 2 0-6 MgO 0-7 TiO 2 0-2. It is preferable that the amount of SiO 2 in the glass frit be between 72 and 80 mole%.
  • the amount of ZnO in the glass frit be less than 5 mole%, more preferably less than I mole %. %. It is preferable that the amount of Al 2 O 3 in the glass be between 1 and 3 mole%. It is preferable that the amount of K 2 O in the glass be between 12 and 20 mole%. It is preferable that the amount of TiO 2 in the glass frit is less than I mole %, more preferably 0%.
  • Example 1 Example 2
  • Example 3 SiO 2 78.0 78.0 77.1 Al 2 O 3 2.5 2.5 2.4 Na 2 O 0.0 0.0 0.4 K 2 O 19.5 14.5 17.4 ZnO 0.0 0.0 0.0 MgO 0.0 5.0 2.5 TiO 2 0.0 0.0 0.25
  • Table I The data shown in Table I is for three exemplary alkali-silicate glass compositions. More specifically, these are potassium-silicate frit glass compositions. After melting, each composition was made into frit by dry ball-milling to a mean particle size of less than 30 ⁇ m, for example, 5 ⁇ m to 20 ⁇ m. The high CTE values and the high softening point required for SOFC sealing material is met by adding an expansion coefficient raising filler to the relatively high viscosity vitreous powdered base glass.
  • Exemplary fillers are an alumina mill, zirconia (CTE ⁇ 120x10 -7 /°C) or leucite K 2 O- Al 2 O 3 - 4SiO 2 (CTE ⁇ 200x10 -7 /°C) addition, 5wt % to 25wt%, preferably 5 to 20wt.
  • the second example is similar in composition to the first example, but has MgO substituted for a portion of potassia. This change resulted in a lower viscosity frit, providing a better flow (than that of Example 1) when frit blends were used at a sealing temperature of 900°C.
  • the glass frit formed by the second exemplary glass composition shown in Table 1 has a softening point at 846°C.
  • composition of the third example is similar in composition to the second example, but it has less MgO and it also contains a small amount of Na 2 O and TiO 2 .
  • Na 2 O and TiO 2 are used as fillers to lower the softening point of the resulting composition.
  • This third example has substantially lower softening temperature than that of Example 1, and lower viscosity.
  • the glass frit formed by the third exemplary glass composition shown in Table 1 has a softening point at 773°C.
  • the sealing material comprises alkali-silica-based glass frit in 80 to 95 weight %, and mill addition 5wt % to 25 wt%, preferably 10 to 20 wt%, such that total wt % of glass frit and the mill addition is 100 wt%. It is preferable that the a mean particle size of the addition be less than 30 ⁇ m, more preferably less than 20 ⁇ m and even more preferably less than 10 ⁇ m. For example, one may use 90:10 blend (wt% basis), such as 90% powdered glass and 10% AlcoaTM alumina with mean particle size of less than 5 ⁇ m and preferably less than 1 ⁇ m, in order to facilitate leucite formation.
  • alumina addition would be to form a small amount of leucite (K 2 O- Al 2 O 3 - 4SiO 2 ) during sealing to increase the CTE of the overall composition to about 100 to 110x10 -7 /°C.
  • leucite K 2 O- Al 2 O 3 - 4SiO 2
  • These CTE values match CTE values of materials used for fuel cell electrodes, interconnects and support structures.
  • the resultant material is crystalline enough that little flow is exhibited until the temperature reaches about 100°C, thus permitting the seal to be functional at operating temperatures up to 1000°C.
  • the first blend comprises glass frit in 80 weight % and 20% zirconia mill addition.
  • the second blend comprised 90 wt % glass frit and 20 wt % leucite mill addition.
  • the third blend comprised 85 wt % glass frit and 15% alumina mill addition.
  • the fourth example of Table 2 comprises frit glass of Example (90 wt%) and leucite (10% wt) addition.
  • Table 2 Glass frit of Glass frit of Glass frit of Glass frit of Glass frit of Ex1/Zirconia Ex1/Leucite Ex1/Alumina Ex3/Leucite Composition wt% 80wt%/20wt% 90Wt%/10wt% 85wt%/15wt% 90Wt%/10wt% Sealing Temperature 900°C 875°C 975°C 750°C *CTE, RT to 500°C 83x10 -7 /°C 105x10 -7 /°C 122x10 -7 /°C 112.9x10 -7 /°C * CTE was measured on sintered samples, the term RT stands for room temperature.
  • Table 2 shows that all three blends produced a seal at the sealing temperature of less than 1000°C.
  • the glass frit/zirconia blend produced lowest seal CTE values.
  • some alumina mill addition may also be added to the mix, in the amount required to raise the CTE of the resultant blend to the required levels.
  • the glass frit/leucite blend had only 10% leucite by wt.
  • the leucite source that was added in order to raise the CTE value of the resultant seal was a glass-ceramic (composition in mole%: Na 2 O 4.7; K 2 O 13.0; Al 2 O 3 18.0; SiO 2 59.1; TiO 2 5.1).
  • this (glass-ceramic) composition was melted at the temperatures between 1600°C to 1650°C, the resultant material was ceramed at 1100° for four hours and then ball-milled to a mean particle size of 10-20 ⁇ m.
  • the resultant glass/leucite blends produced the seals at the lowest firing temperatures (i.e., it has the lowest sealing temperatures of 875°C and 750°C, respectively) of all blends.
  • the mixture formed strong, adherent glassy coatings and sealed well to high CTE substrates (such as E-brite TM and zirconia, for example) at temperatures as low as 750°C.
  • This sealant is potentially less reducable than the other two sealants because it does not contain XnO.
  • the proper stoichiometry for the glass of Example 3 may also be achieved by slow dissolution and homogenization of the second (i.e. Lucite) blend with potassium silicate water glass (for example, Kasil TM 16 (commercially available from the PQ corporation of Philadelphia, PA) by heating at 750°C.
  • the resultant coatings were applied to the e-bright substrate and were glossy, clear and strongly adherent following the homogenization process.
  • the glass frit/alumina blend utilized fine alumina (Alcoa A1000SG, available from Alcola, Pittsburg, PA) as a filler, so that leucite could be formed in situ during firing via reaction between glass frit and the filler, K 2 O -SiO 2 (frit) + ⁇ - Al 2 O 3 (A1000SG) ⁇ K 2 O ⁇ Al 2 O 3 ⁇ 4SiO 2 (leucite).
  • the high CTE of the resultant seal confirms that this reaction did indeed occur (during firing).
  • Figure 4 illustrates the temperature/CTE behavior of the two of the blends depicted in Table 2 (top two curves). It is noted that these blends have higher CTEs and lower viscosity than that of the sealing material (bottom curve) disclosed in U.S. Patent 6,291,092 .
  • the second composition blend depicted in Table 2 was coated on the E-bright TM substrate and fired at 875°C for 1 hour in air. It was then exposed to a simulated SOFC environment, forming gas (97% CO 2 , 3% H 2 ) saturated with steam at 750°C for 2 hours. The resultant seal formed a good interface between the seal and the substrate with no evidence of cracking. The quality of the interface remained unchanged after 200 hour exposure in the simulated SOFC environment
  • potassium silicate frit blends form a seal on high CTE substrates for SOFC at temperatures as low as 750°C.
  • These blends offer excellent compatibility with high-Cr stainless steal alloys without the potential for redox reactions and are unaffected following 200 hour exposure at 750°C in a simulated reducing SOFC environment comprising of forming gas (97% CO 2 , 3% H 2 ) saturated with steam.

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  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Geochemistry & Mineralogy (AREA)
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  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Sustainable Development (AREA)
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  • Fuel Cell (AREA)
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EP06733746A 2005-01-18 2006-01-13 Sealing materials and devices utilizing such materials Expired - Fee Related EP1841705B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US11/038,921 US7189470B2 (en) 2005-01-18 2005-01-18 Sealing materials and devices utilizing such materials
PCT/US2006/001781 WO2006078747A2 (en) 2005-01-18 2006-01-13 Sealing materials and devices utilizing such materials

Publications (3)

Publication Number Publication Date
EP1841705A2 EP1841705A2 (en) 2007-10-10
EP1841705A4 EP1841705A4 (en) 2010-04-28
EP1841705B1 true EP1841705B1 (en) 2011-10-19

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US (1) US7189470B2 (zh)
EP (1) EP1841705B1 (zh)
JP (1) JP5291936B2 (zh)
CN (1) CN101103472B (zh)
CA (1) CA2593765A1 (zh)
TW (1) TW200639138A (zh)
WO (1) WO2006078747A2 (zh)

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US7470640B2 (en) * 2006-04-11 2008-12-30 Corning Incorporated Glass-ceramic seals for use in solid oxide fuel cells
CN101500957B (zh) * 2006-08-07 2012-08-29 池袋珐琅工业株式会社 玻璃衬里用面釉组合物
US8440367B2 (en) * 2006-12-05 2013-05-14 Corning Incorporated Solutions for solid oxide fuel cell seal failures
US20110129752A1 (en) * 2007-05-04 2011-06-02 Dirk Peter Claassen Connection of chemical or thermal reactors
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KR101579308B1 (ko) * 2008-02-25 2015-12-21 가부시키가이샤 노리타케 캄파니 리미티드 세라믹 제품 및 세라믹 부재의 접합 방법
US7989374B2 (en) * 2008-05-15 2011-08-02 Corning Incorporated Non-contaminating, electro-chemically stable glass frit sealing materials and seals and devices using such sealing materials
JP5390148B2 (ja) * 2008-09-16 2014-01-15 一般財団法人ファインセラミックスセンター 熱サイクル耐久性に優れるガスシール部位を有するガスシール構造体及びその製造方法
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JP5238610B2 (ja) * 2009-05-27 2013-07-17 株式会社ノリタケカンパニーリミテド 固体酸化物形燃料電池システムおよび接合材
US7989373B2 (en) * 2009-06-30 2011-08-02 Corning Incorporated Hermetic sealing material
JP5280963B2 (ja) * 2009-08-04 2013-09-04 株式会社ノリタケカンパニーリミテド 固体酸化物形燃料電池用接合材およびその製造方法
JP5469959B2 (ja) * 2009-08-24 2014-04-16 株式会社ノリタケカンパニーリミテド 酸素イオン伝導モジュールならびに該モジュール用シール材およびその利用
EP2890653B1 (en) 2012-08-30 2016-08-24 Corning Incorporated Antimony-free glass, antimony-free frit and a glass package that is hermetically sealed with the frit
JP5973377B2 (ja) * 2013-04-24 2016-08-23 株式会社ノリタケカンパニーリミテド 固体酸化物形燃料電池用グリーンシートおよびその製造方法
JP6756969B2 (ja) * 2016-01-12 2020-09-16 日本電気硝子株式会社 封着材料
JP6942435B2 (ja) * 2016-01-12 2021-09-29 日本電気硝子株式会社 封着用ガラス
CN113461334B (zh) * 2021-06-11 2022-11-18 浙江安力能源有限公司 用于封接钠镍电池的陶瓷隔膜和金属-陶瓷热压封接陶瓷端盖的玻璃焊料及其制备和应用
CN117410517B (zh) * 2023-12-15 2024-03-15 中石油深圳新能源研究院有限公司 固体氧化物燃料电池的密封件及其制备方法

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Publication number Publication date
CN101103472B (zh) 2011-11-23
JP5291936B2 (ja) 2013-09-18
WO2006078747A3 (en) 2006-09-08
EP1841705A4 (en) 2010-04-28
US20060160690A1 (en) 2006-07-20
EP1841705A2 (en) 2007-10-10
JP2008527680A (ja) 2008-07-24
TW200639138A (en) 2006-11-16
CN101103472A (zh) 2008-01-09
US7189470B2 (en) 2007-03-13
CA2593765A1 (en) 2006-07-27
WO2006078747A2 (en) 2006-07-27

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